Polyfunctional carbonyl nitride oxides

ABSTRACT

This invention relates to polyfunctional carbonylnitrile Noxides and their carbonyl hydroximoyl halide and carbonyl nitrolic acid precursors as new compositions of matter.

United States Patent Breslow [451 June 13, 1972 [54] POLYFUNCTIONALCARBONYL NITRIDE OXIDES [72] Inventor: David S. Breslow, MadelynGardens, Del.

[73] Assignee: Hercules Incorporated, Wilmington, Del.

22 Filed: May 13, 1969 [21] App]. No.: 839,123

Related U.S. Application Data [62] Division of Ser. No. 584,113, Oct. 4,1966, Pat. No.

51 Int.Cl ..C07c131/08 [58] FieldofSearch ..260/54S,546,566,584

Primary Examiner-Lorraine A. Weinberger Assistant Examiner-Paul J.Killos Attorney-Emest G. Peterson [57] ABSTRACT 9 Claims, N0 Drawings OMal-se) T 2 POLYFUNCTIONAL CARBONYL NITRIDE OXIDES This application is adivision of copending U.S. Pat. application Ser. No. 584,113, filed Oct.4, 1966, now U.S. Pat. No. 3.504,0 l 7.

In accordance with this invention, a new class of nitrile oxides hasbeen discovered, namely, polyfunctional carbonyl nitrile oxides havingthe general formulas:

l l[ III where R is any organic radical inert to the carbonyl nitrileoxide groups. as, for example, where R is an alkylene, cycloalkylene,arylene, aralkylene, alkarylene, alkylene-diarylene,cycloalkylene-dialkylene arylene-dialkylene, etc. radical such asmethylene, ethylene, trimethylene, tetramethylene, pentamethylene,decamethylene, phenylene, naphthylene, biphenylene, anthrylene,cyclohexylene, phenylethylene, xylylene, phenylenedimethylene,methylenediphenylene, ethylenediphenylene, cyclohexylenedimethylene,etc., or an alkylene-oxy-alkylene, arylene-oxy-arylene,alkarylene-oxyarylene, alkarylene-oxy-alkarylene,aralkylene-oxy-alkylene, aralkylene-oxy-aralkylene, or the correspondingthio radicals, such as methylene-oxy-methylene, ethylene-oxy ethylene,phenylene-oxy-phenylene, methylenephenylene-oxy phenylenemethylene,phenylenemethylene-oxy-methylenephenylene, ethylene-thio-ethylene,phenylene-thio-phenylene, phenylenc methylene-thio-methylenephenylene,etc., and sultones, such as ethylene-sulfonyl-ethylene,mbistmethylencsultonyl) phenylene, etc., and n is an integer greaterthan l. The maximum value for n will, of course, be dependent on thenumber of carbon atoms in R, since the value of It cannot exceed thevalence of R. Preferably, n will be an integer of from 2 to 10.

Exemplary of these polyfunctional carbonyl nitrile oxides are oxalylbis(carbonitrile N-oxide), malonyl bis(carbonitrile N-oxide), succinylbis(carbonitrile N-oxide), adipyl bis-(carbonitrile N-oxide), sebacylbis(carbonitrile N-oxide), 1,2,3,- propane tris(carbonyl carbonitrileN-oxide), 1,2,4-pentane tris-(carbonyl carbonitrile N-oxide),-cyclohexane bis(carbony] carbonitrile N-oxide), p-phenylene bis(acetylcarbonitrile N-oxide), 2,2'-thia-bis(acetyl carbonitrile N-oxide),3,3'-thia-bis(propionyl carbonitrile N-oxide), isophthalyl carbonitrileN-oxide, terephthalyl carbonitrile N-oxide, 4,4'bis(benzoyl carbonitrileN-oxide), 4,4'-methylenebis(benzoyl carbonitrile N-oxide),4,4-oxy-bis(benzoyl carbonitrile N-oxide), 3,3'-thia-bis(benzoylcarbonitrile N-oxide), the ethylene glycol, tetramethylene glycol,hexamethylene glycol, 1,4-cyclohexene glycol, resorcinol, 4,4-dihydroxybiphenylene, isopropylidene-4,4-bisphenol, etc. esters ofcarboxy carbonitrile N-oxide, polymers containing pendant carbonitrileN-oxide groups, as for example, ethylene-acrylic acid copolymers andpartially hydrolyzed poly(alkyl acrylate) where two or more of thependant carboxyl groups have been converted to carbonyl carbonitrile N-oxide groups, etc.

The precursors of these new polyfunctional carbonyl nitrile oxides arelikewise new compounds and have the following general formulas:

where R and n are the same as defined above and Y is halogen, i.e..fluorine, chlorine, bromine, or iodine, or nitro (NO Thesepolyfunctional carbonylhydroximoyl halides and carbonyl nitrolic acidsare readily converted to the corresponding nitrile N-oxide by treatmentwith an alkaline material, such as a tertiary amine, an alkali oralkaline earth metal carbonate, hydroxide, carboxylate, or alkoxide, analkaline earth metal oxide, or zinc oxide, etc.

Thus the new polyfunctional carbonyl compounds of this invention willhave one of the following formulas:

where Z is w r Y is al ge 1 and R is a hydrocarbon radical,hydro-carbon-oxy-hydrocarbon radical, hydrocarbon-thio-hydrocarbonradical, or hydrocarbon-sulfonyl-hydrocarbon, and n is an integergreater than 1.

The new polyfunctional carbonyl hydroximoyl halides having formulas IVand V where Y is halogen can be prepared from poly( haloacetyl)compounds. The latter haloketones are readily produced by the reactionof a poly(acyl halide) with diazomethane to yield a poly(diazoketone),which in turn, on treatment with hydrogen halide, yields the desiredpoly( haloacetyl compound. Exemplary of the acid halides that can be soconverted to such poly(haloketones) are compounds having the formulaXCO(CH ),,,COX where X is halogen and m is O to 10 or higher such as theacid halides of oxalic acid, malonic acid, succinic acid, adipic acid,sebacic acid, etc., and other aliphatic, cycloaliphatic and aromaticpoly(acyl halides) such as l,2,3-propanetricarboxylic acid,l,2,4-pentanetricarboxylic acid, l,4'cyclohexanedicarboxylic acid,2-carboxy-2-methyl-cyclohexaneacetic acid, ethyleneacrylic acidcopolymer, a partially hydrolyzed poly( alkyl acrylate), diglycollicacid, p-phenylenediacetic acid, thiodiacetic acid, thiodipropionic acid,4,4-sulfonyldibutyric acid, phthalic acid, terephthalic acid,4,4'-biphenyl dicarboxylic acid, trimellitic acid, trimesic acid,naphthalic acid, etc.

Poly(haloacetyl) compounds wherein the haloacetyl groups are directlyattached to an aromatic nucleus can also be prepared by introducing twoor more haloacetyl groups by means of a normal Friedel-Crafts reaction.Another method is to chlorinate or brominate a polyacetyl aromaticcompound in which reaction one chlorine or bromine is introduced intoeach methyl group. Typical of the poly(haloacetyl) compounds that can beprepared by one or more of these procedures are l,4-bis( chloroacetyl)benzene l 3 ,5- tris(chloroacetyl)benzene,4,4'-bis(bromoacetyl)biphenyl, 1,5-bis( chloroacetyl )naphthalene, 4 ,4bis(chloroacetyl)diphenyl ether, chloroacetylated polystyrene, etc.

The haloketone compounds are then converted to the hydroximoyl halidesby reaction with an alkyl nitrite and hydrogen halide under anhydrousconditions. Instead of an alkyl nitrite, other nitrosating agents can beused, as for example, N 0 nitrosyl chloride, etc. An alternativeprocedure for preparing the hydroximoyl halides having the formula V isto nitrosate an aliphatic or aromatic polyketone to produce apoly(oximinoketone) which on halogenation yields the poly( carbonylhydroximoyl halide).

The polyfunctional carbonyl nitrolic acids having the formula V where Yis NO can be prepared by the reaction of a polyketone with N 0, whichyields the poly(carbonyl nitrolic acid) directly.

The polyfunctional carbonyl hydroximoyl halides and carbonyl nitrolicacids represented by formula VI above are derived from esters. Thecarbonyl hydroximoyl halides having formula VI where Y is halogen can beprepared by reaction of an amino ester with sodium nitrite and hydrogenhalide to form a diazo ester followed by conversion of the diazo esterwith nitrous acid and hydrogen halide to the hydroximoyl halide. Thus,for example, with glycine or one of its precursors, such asaminoacetonitrile, it is possible to prepare a wide variety of glycinateesters from diols, triols, etc., which can be be converted by this routeto the polyfunctional carbonyl hydroximoyl halides. The carbonylnitrolic acids having formula VI where Y is NO can be prepared frombetaketoesters. For example, acetoacetic acid esters can be readilyprepared by the reaction of diketene with polyols and then nitrosatingthe beta-ketoester with aqueous nitrous acid to yield the correspondingoximinoketoester. Treatment of these compounds with nitric acid givesthe nitrolic acid in excellent yield and treatment of the nitrolic acidwith hydrogen chloride then yields the hydroximoyl chloride. Actually,the reaction can be carried out in one step by reacting theoximinoketoester with a mixture of nitric and hydrochloric acids toyield the hydroximoyl chloride directly.

As pointed out above, the carbonyl hydroximoyl halides and carbonylnitrolic acids having formula IV, V or VI above are readily converted tothe corresponding carbonylnitrile N-oxides having formula I, II or IIIby treatment with an alkaline material Because these carbonylnitrileN-oxides are generally unstable at room temperature and above, if thepure compound is desired, it is necessary to isolate it at lowtemperature, usually in the order of 20 C. or below. Accordingly, formost uses, the nitrile oxide will be generated in situ, as for example,in cross 1inking reactions, as will be demonstrated below.

The following examples illustrate the preparation of the polyfunctionalcarbonyl nitrile oxides and their precursors. All parts and percentagesare by weight unless otherwise indicated.

EXAMPLE 1 A suspension of 32.3 parts of 4,4'-bis(chloroacetyl) diphenylether in I75 parts of diethyl ether was stirred and saturated with dryhydrogen chloride. Then. while slowly passing in hydrogen chloride, 42pans of isoamyl nitrite of 70 percent purity was added in smallincrements with stirring. The solids dissolved as. the nitrite was addedand a clear solution was obtained. The solid, which formed on standingovernight at room temperature, was filtered off. The filtrate wasevaporated to dryness, the resulting mixture of solid and liquid wasfiltered and the solid was washed with a small amount of ether. Thecombined solids amounted to 3 l .8 parts, which is an 83 percent yield.The crude product has a melting point of 188 C. On recrystallizationfrom ether and pentane, it had a melting point of l89- l 90 C. The 4,4'-oxybis(phenylglyoxylohydroximoyl chloride) so obtained has the formula Wi a On analysis, it was found to contain 50.6% C; 2.90% H; 7.71% N; and18.2% Cl. Theory for C I-I Cl N O is 50.4% C; 2.64% H; 7.35% N; and18.6% C].

EXAMPLE 2 A solution of 30 parts of 1,S-dibromo-2,7-dioxo-octane in 140parts of diethyl ether was cooled in an ice bath and saturated with dryhydrogen bromide. To the cooled solution was added 29 parts of isoamylnitrite in small increments. The reaction mixture was allowed to standovernight at room tem perature. The ether was then evaporated and theresidue was recrystallized from carbon tetrachloride. The adipoyl-bis(N-hydroxy formimidoyl bromide) so prepared has the formula:

On analysis, it was found to contain 27.0% C; 2.92% H; 7.50% N; and44.4% Br.

EXAMPLE 3 Tetramethylene glycol was reacted with glycinyl chloridehydrochloride to prepare the bis(glycinate ester). A solution of 69.5parts of this ester in parts of water was cooled in an ice-salt bath and35 parts of concentrated hydrochloric acid was added. To the chilledsolution was then added, in small increments, a solution of 34.5 partsof sodium nitrite in 50 parts of water. The addition of hydrochloricacid and sodium nitrite was then repeated. The white solid whichprecipitated was filtered off, washed with water, dried, and then wasrecrystallized from a benzene-hexane mixture. The tetramethylene bis(ester) of oxalomonohydroximoyl chloride so obtained has the formula:

01 0 9 c1 HO-N kii --o 0H1)4oi (J=NOH On analysis, it was found tocontain 32.0% C; 3.49% H; 9.04% N; and 23.2% C1. Theory for C H N Cl,Ois 31.9% C; 3.35% H; 9.31% N; and 23.6% Cl.

EXAMPLE 4 A suspension of 8.3 parts of bis(4-chloroacetylphenyl methane(melting point of l22.5-124.5 C.) in 50 parts of dioxane was stirred,saturated with hydrogen chloride, and 7.75 parts of isoamyl nitrite(98.6 percent pure) was added in small increments. The reaction mixturewas then stirred with activated carbon, filtered, the diluent strippedoff and the residue was washed with hot carbon tetrachloride. Thecreamcolored, solid produce so obtained amounted to 7.07 parts, an 84.8percent yield. On recrystallization from ether-hexane it has a meltingpoint of l7ll72 C. (d). The 4,4- methylenebis( phenylglyoxylohydroximoylchloride) so produced has the formula On analysis, it was found tocontain 7.47% N and 18.4% Cl. Theory for C,-,l-l, l I O,,Cl is 7.39% Nand 18.7% Cl.

EXAMPLE 5 A suspension of 15.3 parts of 4,4'-bis( chloroacetyl)biphenyl, having a melting point of 23023l.5 C., in 250 parts of dioxanewas sparged with hydrogen chloride and 297 parts of isoamyl nitrite(98.6 percent pure) was added in small increments. The reaction mixturewas then sparged with nitrogen and the diluent was stripped off. Theresidue was recrystallized from dioxane-hexane and then from ethylacetate. The 4,4-bis(phenylglyoxylohydroximoyl chloride) so obtainedamounted to 12.87 parts (76.8 percent yield) and had a melting point of214 C.(d). It has the formula On analysis, it was found to contain 53.0%C; 2.95% H; 7.70% N; and 19.4% Cl. Theory for C I-I N O Cl is 52.6% C;2.76% H; 7.67% N; and l9.4% Cl.

EXAMPLE 6 A mixture of 11.5 parts of ethylene bis(acetoacetate) and l 15parts of 25 percent nitric acid was cooled and 7.2 parts of finelyground sodium nitrite was added. The mixture was then warmed to 30-40C., maintained there for 15 minutes, and poured onto ice. The productwas separated and recrystallized from ether. The ethylene bis(ester ofcarboxynitrolic acid so obtained has the formula Analysis for nitrogenshowed it to contain 19.2 percent. Theory for C l-l N O is l9.0 percentnitrogen.

As pointed out above, the polyfunctional carbonyl nitrile N- oxides ofthis invention are useful as cross-linking agents for unsaturatedpolymers. Any polymer containing ethylenic unsaturation wherein there isat least one hydrogen radical attached to at least one of the carbonatoms of the ethylenic double bond, can be cross-linked with the instantpolyfunctional nitrile N-oxides, in accordance with this invention.Among the polymers which can be cross-linked in this manner arepolybutadiene-1,2; polybutadiene-l,4; styrene--butadiene copolymers;butyl rubber (polyisobutyleneisoprene copolymers); natural rubber;polyester resins such as, for example, maleate containing polyesters;butadiene acrylonitrile copolymers; ethylenepropylenedicyclopentadieneterpolymers; polychloroprene; polyisoprene; alkyd resins such as, forexample, tall oil alkyd resins; polyether copolymers and terpolymerscontaining at least one unsaturated epoxide constituent such as, forexample, propylene oxide-allyl glycidyl ether copolymers and ethyleneoxide epichlorohydrinallyl glycidyl ether terpolymers; and the like.Polymers containing acetylenic unsaturation can also be cross-linked bythe instant process. Mixtures or blends of two or more of suchunsaturated polymers may also be crosslinked by the instant process.

The cross-linking reaction is carried out by contacting the unsaturatedpolymer with a minor amount of the polyfunctional carbonyl nitrileoxide, the amount of the latter depending on the degree of cross-linkingdesired. Generally, an amount of the nitrile oxide of from about 0.01percent, and preferably 0.1 percent. up to about l percent by weight ofthe polymer will be used. Any means can be used for intimatelycontacting the unsaturated polymer with the polyfunctional carbonylnitrile N-oxide. Because of the instability of these carbonyl nitrileoxides at ordinary temperatures, it is usually preferable to generatethe nitrile oxide in situ. This is readily achieved by mixing aprecursor of the polyfunctional carbonyl nitrile oxide, such as itshydroximoyl chloride or nitrolic acid, with the unsaturated polymer andthen treating the mixture with an alkaline material, whereby the nitrileoxide is generated in situ and then cross-links the polymer. Thecrosslinking reaction can be carried out over a wide temperature range,with a temperature of from about -20 C. to about l50 C. generally beingused, and preferably the temperature will be within the range of fromabout 0 C. to about 100 C.

The following examples demonstrate the generation of the polyfunctionalcarbonyl nitrile N-oxide from their precursors and the cross-linking ofunsaturated polymers thereby.

EXAMPLE 7 To a solution of 1 part of an unsaturated polyester, preparedby the reaction of a mixture of maleic and phthalic anhydrides withhydroxyethylated bisphenol, in parts of ethyl acetate was added 0.1 partof the 4,4-oxybis(phenylglyoxylo-hydroximoyl chloride) prepared inExample 1. The solution was stirred and 0.05 part triethylamine wasadded. The solution immediately turned cloudy and gelled within 30minutes.

EXAMPLE 8 Example 7 was repeated except that 0.1 part drops) of l0percent aqueous sodium carbonate was used instead of the triethylamine.Again, the solution gelled within a short time.

EXAMPLE 9 Example 7 was repeated except that the unsaturated polyesterwas dissolved in 5 parts of dioxane and 0.2 part of the4,4'-methylenebis(phenylglyoxylohydroximoyl chloride) prepared inExample 4 was used. The solution was stirred and 0.1 part oftriethylamine was added. The reaction mixture was completely gelledwithin 15 minutes.

EXAMPLE 10 within 30 minutes.

EXAMPLE 1 l Twenty parts of low molecular weightstyrene-butadienerubber, having a molecular weight of about 2,000 andcontaining approximately 66 percent styrene, 3.5 parts of the 4,4-bis(phenylglyoxylohydroximoyl chloride) prepared in Example 5, 10 partsof carbon black, 5 parts of di-octyl)phthalate, 3 parts of anhydrousbarium oxide, and 200 parts of anhydrous tetrahydrofuran were milled ina ball mill under nitrogen for 16 hours. The solvent was removed fromthe fine suspension under reduced pressure at room temperature to yielda creamy paste. Strips l x 4 x Vs inch were cast and allowed to cure atroom temperature in the open atmosphere. After several days, the stripshad cured integrally to a medium hard rubber, which was insoluble inacetone, methyl isobutyl ketone and in methylene chloride.

EXAMPLE 12 sisting of O 0 7) 1 It 7) an: I

whom Z is where Y is halogen or NO R is selected from the group ofhydrocarbon radicals, hydrocarbon-oxy-hydrocarbon radicals,hydrocarbon-thio-hydrocarbon radicals, and hydrocarbon-sulfonylhydrocarbon radicals and n is an integer greater than 1.

2. The composition of claim 1 having the formula 3. The composition ofclaim 2 where R is phenylene-oxyphenylene.

4. The composition of claim 2 where R is phenylenemethylene-phenylene.

5. The composition of claim 2 where R is biphenylene.

6. The composition of claim 1 having the formula 7. The composition ofclaim 6 where R is phenylene oxyphenylene.

8. The composition of claim 6 where R is phenylenemethylene-phenylene.

9. The composition of claim 6 where R is biphenylene.

mg UNITED STATES PATENT OFFICE CERTEFICATE OF CORRECTIUN Patent No. 3670, 023 Dated June 13, 1972 Inventor(s) David BreslOW (Case 39-47) Itis certified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Column 1, line 42 of the printed patent Page 3, line 6 of thespecification cyclohexane should read 1,4-cyclohexane Column 3, line 72of the printed patent Page 7, lines 28 & 29 of the specification, lastsentence, Theory for C H N O Br is 26.8% C; 2.81% H; 7.83% N; and 44.6%Br. is missing.

Column 6, line 15 of the printed patent Page l2 line 9 of thespecification di-octyl) should read di (octyl) In the Claims, Claim 1,the third group f I and R O--C--Z n is missing.

Claim 6, in the formula, C=N should read can Signed and sealed this 31stday of October 1972.

Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissionerof Patents

2. The composition of claim 1 having the formula
 3. The composition ofclaim 2 where R is phenylene-oxy-phenylene.
 4. The composition of claim2 where R is phenylene-methylene-phenylene.
 5. The composition of claim2 where R is biphenylene.
 6. The composition of claim 1 having theformula
 7. The composition of claim 6 where R is phenyleneoxy-phenylene.
 8. The composition of claim 6 where R isphenylene-methylene-phenylene.
 9. The composition of claim 6 where R isbiphenylene.